CN116848079A - Improved stable polyol compositions - Google Patents
Improved stable polyol compositions Download PDFInfo
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- CN116848079A CN116848079A CN202180077950.2A CN202180077950A CN116848079A CN 116848079 A CN116848079 A CN 116848079A CN 202180077950 A CN202180077950 A CN 202180077950A CN 116848079 A CN116848079 A CN 116848079A
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- 150000003077 polyols Chemical class 0.000 title claims abstract description 179
- 229920005862 polyol Polymers 0.000 title claims abstract description 178
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 77
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 54
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 95
- 239000002699 waste material Substances 0.000 claims description 68
- 235000019441 ethanol Nutrition 0.000 claims description 54
- 239000004814 polyurethane Substances 0.000 claims description 32
- 229920000582 polyisocyanurate Polymers 0.000 claims description 25
- 239000011495 polyisocyanurate Substances 0.000 claims description 25
- 239000006260 foam Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 73
- 239000000047 product Substances 0.000 description 26
- 238000007792 addition Methods 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- -1 footwear Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000034659 glycolysis Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Abstract
The present application relates to a process for reducing the acid number of a provided polyol to obtain an improved stable polyol composition, said process comprising the following process steps: dissolving ammonia in a distillable alcohol having a boiling point below 200 ℃ to form an aminated distillable alcohol; providing a polyol having a predetermined acid number; chemically reacting the aminated distillable alcohol with the provided polyol; removing the distillable alcohol by distillation at a temperature of 120-220 ℃; and obtaining an upgraded stable polyol composition having an acid number below the predetermined acid number of the polyol provided.
Description
Technical Field
The present application relates to a upgraded stable polyol composition.
Background
Polyurethanes generally consist of polymers of urethane-linked organic unit chains resulting from the reaction of isocyanate groups with isocyanate-reactive groups, preferably hydroxyl groups. In industry, polyurethane polymers are typically formed by reacting a polyisocyanate with a polyol, wherein the polyisocyanate and polyol each contain an average of two or more functional groups per molecule.
Polyurethanes can be produced in many different forms, from very low density foams to high performance composites, and thus can be used for a variety of purposes: flexible foams, rigid foams, footwear, adhesives, coatings, and more generally elastomers, insulators, construction, and automotive applications. More specific examples of applications include flexible high resilience foam seats, rigid foam insulation boards, electrical potting compounds, high performance adhesives, surface coatings, packaging, surface sealants, and synthetic fibers.
Polyisocyanate (PU) products or Polyisocyanurate (PIR) products used in certain applications have a certain service life, when they should be replaced they can be disposed of as waste. This has a negative impact on the environment.
There is a need for a cost effective method of recycling such PU or PIR waste while respecting the environment.
It is known that PU or PIR products can be converted into polyols by (chemical) reactions. Thus, it is possible to recover part of the waste, such as the polyol.
There are several alternatives such as hydrolysis (addition of water), ammonolysis (addition of ammonia), acidolysis (addition of acid), alcoholysis (addition of alcohol) and glycolysis (addition of ethylene glycol, e.g. DE 2 238 109, DE 2 557 172, DE 2 711 145 and DE 2 834 431). All processes suitable for converting PU/PIR products (waste materials thereof) to polyols are well known to the skilled worker.
In the alcoholysis of PU products, hydroxyl groups in the form of diols and/or triols are used to decompose urethane groups.
Other methods also include dissolving the PU waste in ethylene glycol at high temperature (alcoholysis) and depositing the amine with hydrogen chloride. In addition, it is also possible to dissolve the PU waste in diols, to deposit amines using halogenated esters of phosphoric acid, to remove amine salts and to react with isocyanates (U.S. Pat. No. 3,262).
Unfortunately, the polyols recovered at the end of the extraction process have a relatively high acid number, which is higher than the acid number of the starting materials ("fresh polyol") used to form the initial PU product. When preparing foam, these acids present in the polyol waste may react with the catalyst. When such polyol waste is used in PU or PIR formulations, curing curves, demold times and/or foam properties can be adversely affected. In addition, when polyols having a high acid number are used for the preparation of PU products, several terminal acid groups may form amide bonds in the reaction with polyisocyanates, leading to the formation of carbon dioxide. Thus undesired bubble formation is observed. This will affect the quality of the final product, giving it unsuitable mechanical properties.
This means that the polyol obtained cannot be used in several fields of application, such as the fields mentioned above. Thus, in preparing PU or PIR end products using the polyol obtained, the freedom of choice for the user is low due to the uncertainty of the quality of the polyol used.
Thus, there is a need for further processing of polyol waste, preferably from PU or PIR waste, so that these polyol waste can be recovered as valuable products in PU and/or PIR applications.
The object of the present application is to overcome the above drawbacks and to provide a solution for recycling polyol waste in a simple, cost-effective and environmentally friendly way.
Disclosure of Invention
In this aspect, the present application provides an improved stable polyol composition obtainable by the process steps of:
-dissolving ammonia in a distillable alcohol to form a solution of an aminated distillable alcohol;
-providing a polyol (waste polyol) having a predetermined acid value;
-chemically reacting the ammoniated solution of distillable alcohol with the provided polyol (waste polyol);
-obtaining an upgraded stable polyol composition having an acid number lower than the predetermined acid number of the provided polyol (waste polyol).
In the context of the present application, we note that by applying the process of the present application, polyol waste can be upgraded without the need to use corrosive acids.
It is understood that in order to obtain a PU or PIR product with a certain service life, a "fresh/virgin polyol" with a certain acid number is combined with the polyisocyanate. When these products are no longer used, there are several known methods for recovering the polyol. Acidolysis methods are one example of these methods. At the end of the process, the acid number of the polyol waste is higher than the acid number of the raw material used to provide these initial PU or PIR products, i.e. "fresh/virgin polyol".
In the present application, a method is provided that can reduce the acid value of the recovered polyol (waste polyol), thereby providing a upgraded stable polyol composition having an acid value equal to or lower than the acid value of the recovered polyol (waste polyol). This is particularly advantageous because the upgraded stable polyol composition obtained by the present application can be used directly and thus recycled (preferably excluding the use of strong acids and bases). Thus, the method of the present application is green in this sense and respects the environment. In addition, an additional technical effect provided by the upgraded stable polyol composition of the present application is that its reactivity profile is improved compared to one of the polyol wastes. In addition, the reactivity profile of the upgraded stable polyol composition may be similar or even enhanced compared to the "fresh/virgin polyol", which is particularly advantageous.
In another preferred embodiment, we also note that for certain applications where a low acid number is desired, the polyol waste may also be "fresh polyol" in order to further reduce its acid number. For this purpose, it is also possible to reduce the acid number to 0.03mg KOH/g when using "fresh polyol" or a given polyol waste. This is particularly advantageous. The present application can provide a process that is particularly effective in reducing the acid number of a given polyol, i.e. "fresh/virgin polyol", polyol waste, etc. This particular embodiment may be combined with any of the other embodiments/options mentioned in the present application, including any of the independent and dependent claims mentioned.
The first step of the process of the present application comprises dissolving ammonia in a distillable alcohol to form a solution of an aminated distillable alcohol.
The ammonia mentioned here is preferably in the gaseous state, which is dissolved in the distillable alcohol. The resulting solution may be reacted with a polyol waste material having an acid number. This is a chemical reaction between ammonia and a distillable alcohol, preferably ethylene glycol, thereby reducing the acid number of the polyol waste. Simple physical mixing is insufficient to achieve the effects provided by the present application
The polyol waste material is preferably derived from PU products or PIR products, in particular from used footwear, used elastomers, used PU or PIR foams and mixtures thereof.
The polyols of the present application are advantageously used to provide different types of products such as flexible foams, rigid foams, footwear, adhesives, coatings, and also elastomers, insulators, buildings, structures and automobiles. More specific examples of applications include flexible high resilience foam seats, rigid foam insulation boards, electrical potting compounds, high performance adhesives, surface coatings, packaging, surface sealants, and synthetic fibers.
More precisely, the above-described process suitable for converting PU product or PIR product waste into polyol waste can be used in and is thus part of the present application. All possible processes for recovering polyols from used PU or PIR products are well known to the person skilled in the art.
The chemical reaction between the ammoniated distillable alcohol and the polyol waste, which is in some sense stable enough and upgraded at the end of the process, can reduce the acid number of the polyol waste, which can be directly applied in a number of technical fields. The user is free to integrate the polyol of the present application directly into different PU or PIR systems. Thus, thanks to the process of the application, the useful life of the polyols used as raw materials in the preparation of new PU or PIR products can be prolonged.
Another advantage of the process of the present application is that the process is environmentally friendly compared to the processes known in the art, which makes the present application particularly attractive.
More advantageously, the solution of ammoniated distillable alcohol is added to the polyol waste in an equivalent weight ratio of 0.25 to 3, preferably 0.25 to 2.5, more preferably 1 to 2.2. This embodiment can further reduce the acidity of the final polyol.
According to a preferred embodiment of the present application, separation of the distillable alcohol from the solution after reaction of the ammoniated distillable alcohol solution with the provided polyol waste results in a further decrease in the acid number of the upgraded stable polyol composition.
In this embodiment, the acid number of the polyol of the present application may be reduced to 0.08mg KOH/g, preferably to 0.03mg KOH/g.
In an advantageous embodiment of the application, the moisture content of the upgraded stable polyol composition is lower than the moisture content of the polyol waste, in particular after the step of separating the distillable alcohol.
In a specific embodiment, the reaction between the ammoniated distillable alcohol solution and the provided polyol waste is carried out at a temperature of 70-140 ℃.
Preferably, the reaction of the ammoniated solution of distillable alcohol with the provided polyol waste is carried out at a first temperature of 70-95 ℃, followed by a temperature increase to 95-140 ℃.
More preferably, the solution of ammoniated distillable alcohol comprises 5 to 25 wt. -% ammonia or a derivative thereof, preferably 5 to 20 wt. -%, based on the total weight of the solution of ammoniated distillable alcohol.
Based on this feature, it was noted that a solution was obtained in which ammonia was sufficiently dissolved into the distillable alcohol, which was advantageous when the solution was mixed with polyol waste.
According to a particularly advantageous embodiment of the application, the distillable alcohol is separated from the solution of the ammoniated distillable alcohol at a temperature of 120-220 ℃, more preferably 140-200 ℃, for example by distillation (advantageously under vacuum), thereby removing water and the distillable alcohol.
In a preferred embodiment, the distillable alcohol has a boiling point below 200 ℃.
More preferably, the distillable alcohol is selected from the group consisting of ethylene glycol, methanol, phenol, ethanol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol.
According to another embodiment, the polyol waste is from a used polyurethane/polyisocyanurate product, preferably used footwear, used foam, used elastomer or mixtures thereof. The idea is to recover the polyol from the raw materials that typically must be handled or destroyed. Thus, any waste material of the PU or PIR products may be used to provide the polyol waste material defined in the present application. The polyol waste is preferably derived from PU products or PIR products, in particular used footwear, used elastomers, used PU or PIR foams and mixtures thereof.
As explained above, polyols are used as raw materials to provide PU or PIR products. The acid number of this "fresh/virgin" polyol does not adversely affect the properties of the polyol and can be used directly.
The present application is able to provide a process which can upgrade and stabilize polyol waste, thus forming polyols which can be used directly for new applications and which are effective in terms of the (mechanical) properties obtained.
According to a particular embodiment of the application, the polyol waste is a polyether-based polyol.
In one embodiment of the present application, the upgraded stable polyol composition is further mixed with other compounds selected from the group consisting of surfactants, catalysts, additives, additional polyols, and mixtures thereof to form a polyol blend, wherein the acid number of the resulting polyol blend remains the same (or close) to the acid number of the upgraded stable polyol composition.
The polyols of the present application may be mixed with "fresh/virgin polyol" to provide a polyol blend, which may be further mixed with polyisocyanate.
Regarding the polyol blend, it has been noted that its OH number can be kept stable, so that the stability of the polyol blend over time (OH number and viscosity remain almost constant over time) can be ensured.
Other embodiments of the composition of the application are mentioned in the appended claims.
The application also relates to polyols, preferably polyether polyols, having an acid number of less than 0.45mg KOH/g, preferably less than 0.30mg KOH/g, more preferably less than 0.10mg KOH/g, even more preferably less than or equal to about 0.08mg KOH/g, preferably less than 0.03mg KOH/g.
Other embodiments of the polyol of the present application are mentioned in the appended claims.
The application also relates to the use of the polyols obtained by the process of the application for providing polyurethane or polyisocyanurate products.
Further embodiments of the use of the application are mentioned in the appended claims.
In addition, the present application relates to a process for providing an improved stable polyol composition having an acid number preferably below 0.45mg KOH/g, comprising the steps of:
-dissolving ammonia in a distillable alcohol to form a solution of an aminated distillable alcohol;
-providing a polyol waste material having a predetermined acid number;
-chemically reacting the ammoniated distillable alcohol solution with the provided polyol waste; and
-obtaining an upgraded stable polyol composition having an acid number below a predetermined acid number of the polyol waste.
Accordingly, the present application relates to a process for reducing the acid number of a provided (waste) polyol to obtain an upgraded stable polyol composition, said process comprising the process steps of:
-dissolving ammonia in a distillable alcohol having a boiling point below 200 ℃ to form an aminated distillable alcohol;
-providing a polyol having a predetermined acid number;
-chemically reacting the aminated distillable alcohol with the provided polyol;
-removing the distillable alcohol by distillation at a temperature of 120-220 ℃; and
-obtaining an upgraded stable polyol composition having an acid number below the predetermined acid number of the provided polyol.
For the upgraded stable polyol composition obtainable by the above process, all the technical features described above may also be combined with the features described for the above process, providing an upgraded stable polyol composition having an acid value preferably below 0.45mg KOH/g.
Further embodiments of the method according to the application are mentioned in the appended claims.
In the present application, the term "derivative of ammonia" is understood to mean an amine, which is a compound derived from ammonia by substitution of one, two or three hydrogen atoms with a hydrocarbon group, and having the general structure R 1 NH 2 (primary amine), R 2 NH (secondary amine), R 3 N (tertiary amine).
The distillable alcohol must be able to be distilled easily from the polyol obtained, for example under normal pressure or if desired under reduced pressure. Aliphatic alcohols of 1 to 6 carbon atoms are preferred, and 1 to 3 carbon atoms are preferred. Suitable examples of such alcohols are N-hexanol, N-butanol and t-butanol. Suitable are methanol, ethanol, propanol and isopropanol. Monohydric alcohols in the form of commercial products having a water content of about 4wt% may also be used if desired. Phenol may be used instead of the specific monohydric alcohol. A particularly suitable distillable alcohol may be ethylene glycol.
In the context of the present application, the term "solution of ammoniated distillable alcohol" refers to a solution of ammonia or a derivative thereof dissolved in distillable alcohol. When ammonia is used, the term may be read as "a solution of aminated ethylene glycol" when the distillable alcohol is ethylene glycol. The ammonia is preferably dissolved in ethylene glycol to give a solution of aminated ethylene glycol.
In the present application, the term "available" may be replaced by "obtained".
In the present application, the chemical reaction between the solution of ammoniated glycol and the provided polyol (polyol waste) may be carried out at a temperature of 70-140 ℃. More preferably, the process may be operated in two steps, wherein a first temperature of 70-95 ℃ is applied to the mixture of the solution comprising the ammoniated distillable alcohol and the polyol waste, and then a second temperature of 95-140 ℃ is further applied.
At the end of the process, an upgraded stable polyol composition can be obtained with an acid number below a predetermined value for polyol waste.
In a particularly advantageous embodiment of the present application, it is noted that the OH number and viscosity of the upgraded, stabilized polyol composition obtained according to the present application are stable over time, since their OH number remains stable over a long period of time.
The viscosity of the upgraded, stabilized polyol composition may be 26 to 66.6Pa at 20 ℃.
Acid numbers can be analyzed by Metrohm Autotitrator according to ASTM D4664 and ASTM D7253.
Moisture content can be analyzed by ASTM D203-16 and ASTM D6304 using Metrohm Autotitrator Karl-Fischer.
In the present application, the OH number (also referred to as OH number or OH content) can be measured according to ASTM D1957 standard and expressed in mg KOH/g.
The OH number can be determined by reacting the hydroxyl groups with an anhydride and titrating the liberated acid with a potassium hydroxide solution. The units of OH number are expressed in mg KOH/g polyol. Ohv= (56.1 g/mol KOH x polyol functionality x 1000)/(molecular weight).
According to one embodiment of the application, the polyol waste material is preferably directly reactive with ammonia dissolved in ethylene glycol at a temperature of 80 to about 120 ℃. The solvent ethylene glycol may be distilled off from the reaction mixture under vacuum at a temperature of 120-200 ℃ until the hydroxyl number of the reaction mixture drops to that of the polyol waste. By the process of the present application, the acid value of the polyol waste can be reduced from 0.78mg KOH/g (polyol waste) to 0.08mg KOH/g, preferably to 0.03mg KOH/g, to a upgraded stable polyol composition.
The amount of ammonia dissolved in the ethylene glycol is advantageously 14wt% (preferably 14.4 wt%) based on the total weight of the ammoniated ethylene glycol solution. The aminated glycol may be stored in dark colored bottles in a refrigerator. The solution of aminated glycol is reacted with the polyol waste material at a temperature of 80 to about 120 ℃. Vacuum distillation of ethylene glycol is carried out at a temperature of 120-200 ℃. The polyol waste should be chemically reacted with a solution of ammoniated glycol.
Because ammonia is preferably applied in gaseous form, the moisture content of the upgraded stable polyol composition does not increase. In addition, the distillation step further reduces the moisture content of the upgraded stable polyol composition.
Figure 1 depicts the preparation of aminated ethylene glycol.
In fig. 1, the following reference numerals refer to corresponding parts: 1-PVC pipe; a 2-expansion adapter; 3-receiving adapter; 4-single-neck flask; 5-oil bath; 6-Dreschel wash bottle; 7-PVC pipe; 8-a reactor; 9-funnel; 10-ice bath.
One aspect of the application relates to dissolving ammonia into ethylene glycol. The ammoniated ethylene glycol used in the present application may be prepared by blowing ammonia gas into chilled ethylene glycol. An ammonia stream can be produced from a liquid ammonia solution by heating in a 500ml single neck flask at a temperature of 40-55 ℃. The ammonia stream exiting the flask was passed through a desiccant to dry the ammonia gas. Ammonia gas dried by potassium hydroxide particles was blown (bubbled through) into the frozen ethylene glycol and vigorously stirred with a magnetic stirrer for one hour. The solution was stirred vigorously for 3-4 hours, or until 14% of the ammonia was introduced into the chilled glycol. Ammonia in the prepared ethylene glycol was stored in deep amber bottles at 4 ℃ avoiding sunlight penetration and ammonia loss.
Example 1 shows a first embodiment of the application, preferably describing the dissolution of ammonia in ethylene glycol.
Example 1
In this embodiment, gaseous ammonia chemically reacts with ethylene glycol to form a solution of ammoniated ethylene glycol. Ammonia was dissolved in ethylene glycol. A solution of ammoniated ethylene glycol was prepared by blowing ammonia into chilled ethylene glycol. An ammonia stream can be produced from the liquid ammonia solution by heating the liquid ammonia solution to a temperature of 40 ℃ in a 500ml single-necked flask. The ammonia stream exiting the flask was passed through a desiccant to dry the ammonia gas. Ammonia gas dried by potassium hydroxide particles was blown into the frozen ethylene glycol and vigorously stirred with a magnetic stirrer for one hour. The solution was stirred vigorously for 3-4 hours, or until 14% of the ammonia was introduced into the chilled glycol. Ammonia in the prepared ethylene glycol was stored in deep amber bottles at 4 ℃ avoiding sunlight penetration and ammonia loss.
In a 1L stirred reactor, polyol waste material (moisture content 0.58%) having an acid number equal to 0.78mg KOH/g from used footwear product was provided. To increase the miscibility of the polyol waste, the temperature was gradually raised to 80 ℃. The ammoniated glycol solution was added to the polyol waste at a weight ratio of 2:1 at a stirrer speed of 300rpm and a temperature of 80 ℃. The reaction temperature was raised to 120℃over 1-2 hours. The acid value of the resulting polyol composition was measured to be 0.21mg KOH/g.
In a preferred embodiment, the acid value of the polyol obtained may be further reduced to 0.08-0.21mg KOH/g by gradually increasing the temperature to 200℃to distill ethylene glycol from the polyol obtained. The moisture content of the polyol after distillation was equal to 0.44%.
Example 2-reactivity curves in footwear applications
In Table 1 below, the reactivity curves of three rigid foam compositions are described, as tested in accordance with the PU foam cup test of ASTM D7487.
A standard polyol blend is provided by mixing 80-90wt% of a "fresh polyol" having an OH number of 28mg KOH/g and a functionality of about 3 with 1.5wt% of Niax L6900 silicone surfactant, 2wt% of triethylenediamine catalyst, 0.5wt% water, and other additives. The mixture was blended at 3000rpm to form a standard polyol blend, which was further mixed with polyisocyanate-Suprasec 2444.
By mixing the same components as described previously, the same formulation (20% by weight of recycled polyol, second column in Table 1) was obtained, except that the "fresh polyol" was replaced by a polyol waste (obtained by acidolysis) having an OH number of 44mg KOH/g, added in an amount of 20% by weight. The weight ratio of "fresh polyol"/polyol waste in the polyol blend is from 90/10 to 80/20 based on 100wt% of the polyol blend.
In the third column of Table 1, the use of the polyols obtained according to the application is noted. The composition and the addition amount of the above-mentioned polyol waste are the same as those of the polyol waste except that the polyol waste is treated in the method of the present application to reduce the acidity thereof.
Table 1 below summarizes the properties of the foams obtained.
TABLE 1
Foaming time refers to the time required for the reaction mixture to change from a liquid state to a milky state and then to begin foaming (expansion).
Contact time refers to the time from the beginning of pouring to the top of the foam that can be contacted without breaking.
Free rise density refers to the density measured under normal pressure conditions according to ASTM D7487 for a sample of foam prepared.
Comparative example 1
Example 1 was repeated except that the polyol waste and the aminated ethylene glycol were physically blended (instead of being chemically blended). The acid value of the resulting polyol was 0.99mg KOH/g.
Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. Thus, the appearances of the phrase "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same scheme, but may. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments as would be apparent to one skilled in the art from the present disclosure. Also, while some embodiments described herein include some features included in other embodiments but not others, combinations of features of different embodiments are within the scope of the application and form different embodiments, as will be fully understood by those of skill in the art. For example, in the appended claims, any of the embodiments claimed may be applied in any combination.
As used herein, the singular forms of indefinite and definite articles include both the singular and the plural unless the context clearly dictates otherwise. For example, "isocyanate" refers to one or more isocyanates.
The terms "comprising," "including," and "consisting of …" are synonymous with "comprising," "including," or "containing," and are both closed or open ended, and do not exclude additional ingredients, elements, or method steps not recited. It will be understood that the terms "comprising," "including," and "consisting of …" as used herein, include other terms of the same meaning. This means that the foregoing terms "comprising", "including" and "consisting of …" may preferably be substituted with other terms of the same meaning.
Throughout this application, the term "about" is used to refer to a value that includes the standard deviation of the error of the device or method used to determine the value.
As used herein, the terms "% wt", "wt.%," weight percent "or" weight percent "are used interchangeably.
The recitation of numerical ranges by endpoints includes all integers and suitable fractions within that range (when referring to, for example, the number of elements, 1 to 5 may include 1,2, 3, 4, and when referring to, for example, the measured value, 1 to 5 may also include 1.5, 2, 2.75, and 3.0, 3.80). The description of endpoints also includes the endpoint itself (e.g., 1.0-5.0 includes 1.0 and 5.0). Any numerical range recited herein includes all sub-ranges subsumed therein.
All references cited in this specification are incorporated herein by reference in their entirety. In particular, the teachings of all references specifically cited herein are incorporated by reference.
Unless otherwise defined, all terms used in disclosing the present application, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this application belongs. By way of further guidance, term definitions are also given to better understand the teachings of the present application.
In the present application, the different aspects of the application are defined in more detail. Each aspect so defined may be combined with any other aspect unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous. Although the preferred embodiments of the present application have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the application as disclosed in the accompanying claims.
Claims (15)
1. A method of reducing the acid number of a provided polyol to obtain a upgraded stable polyol composition, the method comprising the process steps of:
-dissolving ammonia in a distillable alcohol having a boiling point below 200 ℃ to form an aminated distillable alcohol;
-providing a polyol having a predetermined acid number;
-chemically reacting the aminated distillable alcohol with the provided polyol;
-removing the distillable alcohol by distillation at a temperature of 120-220 ℃; and
-obtaining an upgraded stable polyol composition having an acid number below the predetermined acid number of the provided polyol.
2. The process of claim 1, wherein the aminated distillable alcohol is added to the provided polyol in an equivalent weight ratio of 0.25-3, preferably 0.25-2.5, more preferably 1-2.2.
3. The method of claim 1 or 2, wherein the polyol provided is a waste polyol.
4. The method of any of the preceding claims, wherein the moisture content of the upgraded stabilized polyol composition is lower than the moisture content of the provided polyol.
5. The process of any one of the preceding claims, wherein the step of removing the distillable alcohol by distillation is carried out at a temperature of 140-200 ℃ ultimately by distillation or under vacuum to remove water and the distillable alcohol.
6. The process of any of the preceding claims, wherein the chemical reaction between the aminated distillable alcohol and the provided polyol is carried out at a temperature of 70-140 ℃.
7. The process of claim 6, wherein the reaction is carried out at a first temperature of 70-95 ℃ followed by an increase in temperature to 95-140 ℃.
8. The process of any of the preceding claims, wherein the ammoniated distillable alcohol comprises 5 to 25wt% ammonia or its derivative, preferably 5 to 20wt%, based on the total weight of the solution of the ammoniated distillable alcohol.
9. The process of any of the preceding claims wherein the distillable alcohol is selected from the group consisting of ethylene glycol, methanol, phenol, ethanol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol.
10. The process of any of the preceding claims wherein the polyol provided is a waste polyol derived from a recycled used polyurethane/polyisocyanurate-based product, preferably used footwear, used elastomer or used foam.
11. The method of any of the preceding claims, wherein the polyol provided is a waste polyol selected from polyether-based polyols.
12. The method of any of the preceding claims, wherein the upgraded stable polyol composition is further mixed with other compounds selected from the group consisting of surfactants, catalysts, additives, and mixtures thereof, and wherein the acid number after mixing the compounds remains equal to or close to the acid number of the upgraded stable polyol composition prior to mixing the compounds.
13. The process of any of the preceding claims, wherein the acid number of the upgraded stable polyol composition is below 0.45mg KOH/g, preferably below 0.30mg KOH/g, more preferably below 0.10mg KOH/g, even more preferably equal to or below about 0.08mg KOH/g, advantageously below 0.03mg KOH/g.
14. A stable polyol composition for converting waste polyols into a quality-improving, having an acid value of less than 0.45mg KOH/g, preferably less than 0.30mg KOH/g, more preferably less than 0.10mg KOH/g, even more preferably equal to or less than about 0.08mg KOH/g, advantageously less than 0.03mg KOH/g.
15. Use of the polyol obtained by the process of any of claims 1 to 13 or the polyol of claim 14 for providing a polyurethane or polyisocyanurate product.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN202011050656 | 2020-11-20 | ||
| IN202011050656 | 2020-11-20 | ||
| EP21150651.4 | 2021-01-08 | ||
| PCT/EP2021/082166 WO2022106552A1 (en) | 2020-11-20 | 2021-11-18 | Upgraded stabilized polyol composition |
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| CN116848079A true CN116848079A (en) | 2023-10-03 |
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| CN202180077950.2A Pending CN116848079A (en) | 2020-11-20 | 2021-11-18 | Improved stable polyol compositions |
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